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Combines the performance of plastics with environmental sustainability.

Combines the performance of plastics with environmental sustainability. P&G’s Nodax . Biodegradable thermoplastics from renewable resources. Nodax TM Project. Overall Objective

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Combines the performance of plastics with environmental sustainability.

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  1. Combines the performance of plastics with environmental sustainability.

  2. P&G’s Nodax Biodegradable thermoplastics from renewable resources

  3. NodaxTM Project Overall Objective Produce a novel and functional polymer from a renewable resource that is competitive with conventional petroleum-based polymers in price, and offers improved end-use properties. Approach Thermoplastic aliphatic polyester (NodaxTM) production in microorganisms or agricultural crops to achieve price and volume objectives. Commercialization • Broadly license and transfer R&D for production of neat polymer, resins and forms. • Create demand by internal use and broad licensing of other end users. • Cooperate and collaborate with other companies to capitalize on synergies with other bioplastics to grow entire market.

  4. NodaxTM - P&G Bioplastics Materials Properties • Comparable to high-grade polyethylene • Strength, flexibility, toughness • Additional beneficial characteristics of polyesters • Dyeability, printability, compatibility, etc. • Gas Barrier properties combined with heat sealability • Hard springy elasticity upon stretching • Chemically digestibility in hot alkaline solutions Additional Features • Produced from renewable resources • Fully biodegradable and compostable • Novel and proprietary materials Estimated Cost • $ 1.00 - $ 2.50/kg. (Target) • Competitive with high-end commodity plastics

  5. Historical Background Issues • P&G’s detergent phosphate experience 1970 ~ • Increasing solid Waste concerns 1980 ~ • Are we running out of landfills? • Plastic packages, diapers and other disposable products Technical Approach • Biodegradable/compostable plastics 1990 ~ • Disintegration to pieces • Mineralization to CO2, CH4, and H2O Specific Actions • Quick fix with available materials • Starch-based resins • Cellulose derivatives • Long-term solution • Next generation degradable polymers • Major technical discontinuity

  6. Polyhydroxyalkanoates (PHAs)

  7. Properties of Conventional PHAs Biopol™ • Commercial PHA from Metabolix • Bacterial fermentation of sugar Advantages • Produced from renewable resources • Biodegradable (compostable) • Thermoplastic • Moisture resistant Limitations • Cost $5 ~ $8/lb? • Supply Limited production scale • Pollution Biomass disposal • End-use properties Hard, brittle, weak, unstable • Processability High Tm, poor thermal stability Low extensional viscosity Slow crystallization rate

  8. Branched PHAs (Nodax)

  9. NMR Spectrum of Nodax Produced by Pseudomonas sp. 61-3

  10. PHA Copolymer Compositions Literature Metabolix Literature Literature Metabolix Kaneka P&G P&G P&G P&G P&G P&G P&G claimed the use of C4C6in films, fibers, nonwovens, hygiene products, etc. C4’s level is at least 50% P&G also claimedall PHA opolymers with 5 components and above

  11. Properties of NodaxTM Biological Properties • To be made from renewable resources • Biodegradable - aerobic, anaerobic Thermo-mechanical Properties • Similar to polyethylene, polypropylene • Versatility - films, fiber, elastomers, etc. • Exhibit hard (springy) elasticity Physico-chemical Properties • Affinity/compatibility with certain materials • Higher surface energy - printing, adhesion • Hot alkali digestibility • Barrier properties • UV resistance, high density, etc.

  12. Biodegradable Summary Aerobically Degradable: Compost, surface exposure • 78% / 45 days via intensive aerobic compost simulation. Anaerobically Degradable: Septic, sediment, marine • Good in simulated landfill conditions. Same rate or better than reference materials like yard waste, various papers. • Good in septic systems. Disintegration in 7 days in model system. • Slower in marine conditions. 40% / 40 days. Reference material was 55% / 15 days.

  13. Mineralization of NodaxTM

  14. Mineralization of NodaxTM

  15. Thermal Properties Melting • C2 branches (PHBV) do not affect Tm much • C3 branches (NodaxTM) depresses Tm • Branch size above C3 has less effect on Tm lowering efficacy Crystallinity • C2 branches has little effect on total crystallinity • NodaxTM has the same crystal structure as PHB • C3 branches depresses crystallinity • Larger branches depresses crystallinity • Higher branch content slows down crystallization rate Glass Transition • Higher branch content depresses Tg • Larger branches depresses Tg

  16. Melt Temperature

  17. Crystallinity

  18. Mechanical Properties Young’s Modulus (Stiffness) • Content and size of branches reduce modulus • Between HDPE and LDPE • Molecular weight has little effect • Aging slightly increases modulus Yield Stress • Content and size of branches reduce yield stress • Between HDPE and LDPE • Molecular weight has little effect Toughness and Ultimate Elongation • Molecular weight has profound effect (preferably > 600K) • Size of branches improves both Comparable to high-grade PE

  19. Tensile Properties

  20. Tensile Properties

  21. Interactions with Other Materials Bulk Phase Properties • Solubility – “green” non-CFC solvents (acetone, ethyl acetate, etc.) • Compatibility – plasticizers, antioxidants, processing aids • Blendability, miscibility • Dyeability • Moisture and grease resistance • Barrier – O2, CO2, odor Surface Properties • Adhesion • Dispersibility • Wettability • Printability

  22. Polylactic acid Physical Properties Often amorphous Transparent Brittle, hard, and stiff Use temperature < 60° C Degradation Mechanisms Hydrolytic attack Not directly biodegradable Temperature, pH, and moisture effect Spontaneous degradation Processability Quick quench Fiber spinning Polyhydroxyalkanoates Semicrystalline Tough, ductile and drapable Usually opaque Use temperature < 120º C Enzymatic digestion Rapid biotic degradation Aerobic or anaerobic conditions Relatively stable in ambient Slow crystallization Films, fibers PLA vs. PHA (NodaxTM)

  23. Dyeability Dyeability test • Immersion of films in aqueous dispersion of nonionic dye • Similar to commercial polyester fiber dyeing process

  24. Heat Sealability

  25. Gas Permeability of Films Transmission Rate PolymerMoistureO2 Saran 1 10 NodaxTM90 40 PET 50 60 Polypropylene 10 2300 Polyethylene 20 7000 Bionolle 300 Natural rubber 1000 24000 Cellulose acetate 3000 1000 Margin of error 0.5x - 2x For most polymers, CO2 permeability is ~ 5x O2 permeability

  26. Chemical Digestibility Alkaline DIgestion • Hot alkaline solutions attack bioplastics • Caustic solution, e.g., Cascade • Rapid disintegration to particulate • Degradation to water-solubles (monomer, oligomer) • Full biodegradation of digested products Implications • Flushable after digestion • Household digestion possible • Institutional uses: • Fast-food restaurants, hospitals, marine transportation, military use • Specialty uses: • Electronic circuit board, mold release, etc.

  27. Key Attributes of NodaxTM • Excellent barrier for odor, oxygen, CO2, and moisture • Impervious to grease, water, and other liquids • Heat-sealable, thermally processable • Good PE-like mechanical properties • Alkali digestible (e.g., with Cascade solution) • Dyeable and printable • Compatible with various additives and fillers • Made into laminated paper, layered plastic sheets, nonwovens, etc. • Blendable with many other polymers • Low cost, when made by crop plants • Available from renewable resources • Biodegradable, compostable

  28. Conversion to Formed Articles • Films and sheets • Molded articles • Fibers • Elastics • Laminates and coated articles • Nonwoven fabrics • Synthetic paper products • Foams

  29. ElastomericFilm (Gloves)High MW (1MM+) Blown Films(Garbage Bags) Blow Molding(Rigid Packaging) Thermoforming Spun-bond NW Foam(cups) Tie-Layer Cast orTintered Films(e.g., breathable) Functional Fiber(Melt Spun) Adhesives Coating/Lamination(Melt Resin)(e.g., coated paper, NW) Synthetic Paper Melt Blown NW Injection Mold High MW (700M) Low MW (500M) 5% 10% 15% Stiff/Brittle Flexible/Ductile Soft/Elastic Composition (Comonomer Content)

  30. Protoypes of NodaxTM Products

  31. Paper Laminates/Coatings • Shows good adhesion to paper,cellulosics • Water/grease barrier • Heat sealable • More flexible and crack resistantthan PHB/PHBV • Repulpable Navy Drinking Cup Application: • Heat sealing rate sufficient for drinking cups to be processed at production speeds • Extrusion coating rheology is acceptable • Crystallization rate of neat material needs to be adjusted

  32. NodaxTM Foam Clam-shell containers made of NodaxTM foam

  33. NodaxTM Fiber Nodax bicomponent fiber

  34. Combines the performance of plastics with environmental sustainability.

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